TiO2(B)表面修饰富锂层状氧化物Li(Li0.17Ni0.2Mn0.58Co0.05)O2正极材料

doi:10.15541/jim20140047

摘要/Abstract

摘要：

采用喷雾干燥法和沉淀法, 制备了表面修饰TiO₂(B) (2wt%、4wt%、6wt%和8wt%)的富锂层状氧化物Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂正极材料。X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)结构测试分析结果表明, 修饰TiO₂(B)后样品的体相结构仍然保持初始样品的层状结构, 仅氧化物颗粒表面附着有少量TiO₂(B)纳米晶。示差扫描量热测试(DSC)表明, 与初始样品比较, 修饰TiO₂(B)后样品的热稳定性得到明显改善。在2.0~4.8 V范围内进行恒流电化学性能测试。研究显示, 在0.1C(1C=300 mA/g)倍率下, 修饰4wt%TiO₂(B)样品的首次放电比容量可达296.4 mAh/g, 首次库伦效率则由初始样品的77.7%提升到修饰TiO₂(B)后样品的84.3%, 100周循环后电极容量保持率由初始样品的69.5%提升到修饰TiO₂(B)后样品的80.2%。即使在阶梯倍率的2C倍率下, 修饰4wt%TiO₂(B)的样品仍具有较高的电化学容量(166.5 mAh/g)。以上研究结果表明, 表面修饰TiO₂(B)纳米晶可以显著改善富锂层状氧化物Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂的热稳定性和电化学性能。

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关键词: 锂离子电池, 正极, 富锂层状氧化物, 表面修饰, TiO2(B)

Abstract:

The Li-rich layered Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂ oxide was prepared by a spray-drying method. Subsequently, the surface modification with TiO₂(B) nanocrystallites (2wt%, 4wt%, 6wt%, 8wt%) was introduced into the Li-rich layered Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂ oxide by precipitation method. It is demonstrated that there is no obvious change in the crystallographic structure of the Li-rich layered Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂ oxide based on the analysis of XRD, SEM and TEM, while only the surface of the oxide is modified with TiO₂(B) nanocrystallites. It is indicated from DSC curves that the thermal stability of Li-rich layered oxide is obviously improved by the surface modification with TiO₂(B) nanocrystallites. Correspondingly, the large discharge capacity of 296.4 mAh/g and high coulombic efficiency of 84.5% are obtained at 0.1C rate (1C=300 mA/g) in the first cycle for the Li-rich layered oxide after the surface modification with TiO₂(B) nanocrystallites (4wt%). Moreover, the capacity retention after 100 cycles is increased from 69.5% for the pristine sample to 80.2% for the TiO₂(B)-modified sample. Even at 2C rate, the large discharge capacity of 166.5 mAh/g is still obtained for the TiO₂(B)-modified sample. Apparently, it is demonstrated from the above results that the surface modification with TiO₂(B) nanocrystallites can improve the thermal stability and electrochemical performance of the Li-rich layered Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂ oxide.

Key words: lithium ion battery, cathode, Li-rich layered oxide, surface modification, TiO2(B)

中图分类号:

TM912

刘沁, 袁文, 高学平. TiO₂(B)表面修饰富锂层状氧化物Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂正极材料[J]. 无机材料学报, 2014, 29(12): 1257-1264.

LIU Qin, YUAN Wen, GAO Xue-Ping. Surface Modification of Li-rich Layered Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂Oxide with TiO₂(B) as the Cathode for Lithium-ion Batteries[J]. Journal of Inorganic Materials, 2014, 29(12): 1257-1264.

图/表 10

图 1 初始样品和不同TiO2(B)修饰量样品的XRD图谱

Fig. 1 XRD patterns of as-prepared sample (a) and the samples (b-e) modified with different TiO2(B) contents

图2 初始样品和不同TiO2(B)修饰量样品的SEM照片

Fig. 2 SEM images of samples modified with different TiO2(B) contents (a)As-prepared; (b) 2wt%; (c) 4wt%; (d) 6wt%; (e) 8wt%

图3 初始样品(a)和修饰4wt% TiO2(B)样品(b)的TEM照片

Fig. 3 TEM images of as-prepared sample (a) and the sample modified with 4wt% TiO2(B) (b)

图 4 在充电到4.8 V后, 初始样品和不同TiO2(B)修饰量样品的DSC曲线

Fig. 4 DSC profiles of the samples modified with different TiO2(B) contents after charging to 4.8 V (vs Li/Li+)

图 5 初始样品(a)和4wt% TiO2(B)修饰样品(b)的循环伏安曲线(CV)

Fig. 5 Cyclic voltammorgrams of the as-prepared sample (a) and the sample modified with 4wt% TiO2(B) (b) at scan rate of 0.1 mV/s

图 6 初始样品(a)和4wt%TiO2(B)修饰样品(b)的初始充电曲线和不同循环周次的放电曲线(0.1C倍率下)

Fig. 6 Initial charge curves and subsequent discharge curves of the as-prepared sample (a) and the sample modified with 4wt% TiO2 (B) (b) at different cycles (0.1C rate)

图7 在0.1C倍率下, 初始样品和不同TiO2(B)修饰量样品的循环性能

Fig. 7 Cycle performance of the samples modified with different TiO2(B) contents at 0.1C rate

表 1 初始样品和不同TiO2(B)修饰样品的首周充放电数据

Table. 1 Electrochemical data of TiO2(B)-modified samples in the first cycle (0.1C rate)

TiO₂(B) content	Initial charge capacity / (mAh·g^-1)	Initial discharge capacity / (mAh·g^-1)	Initial irreversible capacity loss / (mAh·g^-1)	Initial coulombic efficiency	Capacity retention after 100 cycles
0	384.2	298.7	85.5	77.7%	69.5%
2wt%	347.7	286.5	61.2	82.4%	79.1%
4wt%	351.7	296.4	55.3	84.3%	80.2%
6wt%	333.6	263.6	70.1	79.0%	78.9%
8wt%	326.0	255.9	106.1	78.5%	78.0%

图8 在1C倍率下, 初始样品和不同TiO2(B)修饰量样品的循环性能

Fig. 8 Cycle performance of the samples modified with different TiO2(B) contents at 1C rates

图9 在不同电流密度下, 不同TiO2(B)修饰量样品的倍率性能

Fig. 9 Rate capability of and the samples modified with different TiO2(B) contents at varied rates

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TiO₂(B)表面修饰富锂层状氧化物Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂正极材料

Surface Modification of Li-rich Layered Li(Li_0.17Ni_0.2Mn_0.58Co_0.05)O₂Oxide with TiO₂(B) as the Cathode for Lithium-ion Batteries

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